Supramolecular Complex of Chlorophyll-<i>a</i> Derivative with <i>N</i>-Protected Histidine through Two-point Binding

Tamiaki, Hitoshi; Kamatani, Yusuke; Nakamura, Soichi

doi:10.1246/cl.190330

Cited by 3 publications

(2 citation statements)

References 12 publications

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“…To mimic the specific interaction of Chls with peptides, we have already reported the complexation of a zinc Chl‐ a derivative Zn‐ 2 (the left drawing of Figure 1) with an N ‐protected histidine, N α ‐fluorenylmethyloxycarbonyl‐ N τ ‐trityl‐L‐histidine [Fmoc‐His(Trt)‐OH] in chloroform 17 . The histidyl imidazolyl group axially ligated the central zinc atom of Zn‐ 2 , and concomitantly the histidyl carboxy group hydrogen‐bonded with the peripheral amino group to form the complex of Zn‐ 2 with Fmoc‐His(Trt)‐OH via the two‐point interaction.…”

Section: Introductionmentioning

confidence: 99%

“…To mimic the specific interaction of Chls with peptides, we have already reported the complexation of a zinc Chl-a derivative Zn-2 (the left drawing of Figure 1) with an N-protected histidine, N α -fluorenylmethyloxycarbonyl-N τ -trityl-L-histidine [Fmoc-His(Trt)-OH] in chloroform. 17 The histidyl imidazolyl group axially ligated the central zinc atom of Zn-2, and concomitantly the histidyl carboxy group hydrogen-bonded with the peripheral amino group to form the complex of Zn-2 with Fmoc-His (Trt)-OH via the two-point interaction. The ligation from the upper and lower sides of the chlorin π-plane produced an asymmetry around the central zinc atom due to the unsymmetrical configuration of the peripheral substituents, which was consistent with the epimerically different αand β-ligations of Chls in natural systems.…”

Section: Introductionmentioning

confidence: 99%

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Recognition of histidines with a synthetic zinc amino‐oxochlorin regioisomer via synergetic coordination and hydrogen bonding

Yuasa,

Hara,

Tamiaki

2024

J of Physical Organic Chem

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Zinc 13‐(N,N‐diethylamino)methyl‐3,3,7,8,12,17,18‐heptaethyl‐2‐oxochlorin was prepared from 2,3,7,8,12,13,17,18‐octaethylporphyrin via the regioselectively acid‐catalyzed double dehydration of cis‐12,13‐diethyl‐cis‐12,13‐dihydroxy‐2‐oxobacteriochlorin to the corresponding 12‐ethyl‐13‐vinyl‐2‐oxochlorin. The synthetic zinc amino‐oxochlorin was axially ligated with the imidazolyl group of Nα‐protected histidines in chloroform, and concomitantly the amino group of the former was hydrogen‐bonded with the carboxy group of the latter. The resulting two‐point bonding supramolecules served as models for the complexes of chlorophylls with peptides in photosynthetic apparatuses including light‐harvesting antennas and charge‐separating reaction centers. A similar 1:1 complex was produced by the interaction of the zinc amino‐chlorin with the related methionine possessing thioether and carboxylic acid moieties.

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Section: Introductionmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

Recognition of histidines with a synthetic zinc amino‐oxochlorin regioisomer via synergetic coordination and hydrogen bonding

Yuasa,

Hara,

Tamiaki

2024

J of Physical Organic Chem

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Two-point connected complex of zinc aminoporphyrin with histidine protected at α-amino and imidazolyl-π nitrogen atoms

Yuasa,

Nakamura,

Tamiaki

2024

Bulletin of the Chemical Society of Japan

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Zinc porphyrins possessing an (N,N-dialkylamino)methyl group at the peripheral position were prepared from β-octaethylporphyrin. The synthetic zinc aminoporphyrins were complexed with an Nα,Nim(τ)-protected histidine through the coordination of the histidyl imidazolyl-τ nitrogen atom with the central zinc atom and the concomitant hydrogen bonding of the histidyl carboxy group with the peripheral amino group. The 1:1 complexation in the chloroform was dependent on the size of the alkyl groups on the peripheral aminomethyl nitrogen atom. The diethyl substitute complexed more strongly than the dimethyl and dipropyl counterparts. The complexation of zinc (diethylamino)methyl-porphyrin with an Nα,Nim(π)-protected histidine was 260-fold stronger than that with the above Nα,Nim(τ)-protected histidine to exhibit the association constant of 2.6 × 106 M−1. The significant enhancement was ascribable to the less sterically demanding and more coordinating Nim(τ)-atom compared with the Nim(π)-atom. The achiral zinc aminoporphyrin was complexed with the chiral Nα,Nim(π)-protected histidine to give a circular dichroism active species in a visible Soret region.

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Sterically controlled and pH-dependent self-aggregation of synthetic zinc 3-(alkylamino)methylated chlorophyll-a derivatives in aqueous micellar solution

Watanabe

Nakamura

Tamiaki

2020

J. Porphyrins Phthalocyanines

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Zinc methyl 3-(methyl/ethylamino)methyl-pyropheophorbides-[Formula: see text] were prepared as models of photosynthetically active bacteriochlorophyll-[Formula: see text] possessing the 3[Formula: see text]-hydroxy group. The synthetic methylamino analog predominantly dimerized via two Zn[Formula: see text]N coordination bonds in aqueous Triton X-100 micelles, while the more sterically crowding and less coordinating ethylamino derivative self-aggregated to form large oligomers through single coordination and hydrogen bonds, Zn[Formula: see text]N–H[Formula: see text]O=C-13, similarly as in the natural self-aggregates of bacteriochlorophyll-[Formula: see text]. The artificial self-aggregates were dependent on the aqueous pH, but the dimer was less pH-sensitive and also more tolerant to the additional Triton X-100.

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Supramolecular Complex of Chlorophyll-a Derivative with N-Protected Histidine through Two-point Binding

Cited by 3 publications

References 12 publications

Recognition of histidines with a synthetic zinc amino‐oxochlorin regioisomer via synergetic coordination and hydrogen bonding

Recognition of histidines with a synthetic zinc amino‐oxochlorin regioisomer via synergetic coordination and hydrogen bonding

Two-point connected complex of zinc aminoporphyrin with histidine protected at α-amino and imidazolyl-π nitrogen atoms

Sterically controlled and pH-dependent self-aggregation of synthetic zinc 3-(alkylamino)methylated chlorophyll-a derivatives in aqueous micellar solution

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